Molecular complexes 1a – 1c, of 4-cyanophenylboronic acid, 1, with N-donor compounds, 4,4'-bipyridine (a), 1,2-bis(4-pyridyl)ethene (b) and melamine (c), respectively, have been prepared, in the form of single crystals, by slow solvent evaporation method. Three-dimensional structures of all the complexes have been determined by X-ray diffraction technique. All the complexes 1a – 1c were noted to be crystallized as hydrates. Variations in the patterns of intermolecular interactions amongst the complexes and also the geometrical features of 1 have been analysed comparing with the features found in the native structure of 1 by determining its crystal structure also. -B(OH)2 moiety in the native form of 1 and also in the molecular complexes, 1a – 1c, adopts syn - anti conformation. Further, calculations were performed, using DFT-D3 method, to rationalize the propensity of formation of hydrate structures and to deliberate the observed structural features with respect to the strength of the intermolecular interactions, for instance, hydrogen bonds.